Continuous process of treating hydrocarbon products



Nov. 28, 1933. w LEL EMA N 1,936,633

CONTINUOUS PROCESS OF TREATING HYDROCARBON PRODUCTS Filed Sept. 21, 1931 i W K 5% O Fax/110E FaR H 3 00501; 6mm

$ x wk g INVENTOR ATTORNEY Patented Nov. 28, 1933 CONTINUOUS PROCESS OF TREATING HYDROCARBON PRODUCTS William Lelgemann, Newark, N. J.

Application September 21, 1931 Serial No. 564,141

9 Claims.

This invention relates to a process for'treating an oil or oils or material containing the same, such as petroleum and other mineral oils, shale oil, etc. and distillates, fractions or resi-'- dues obtained therefrom or admixed therewith and other hydrocarbons and hydrocarbonaceous mixtures of relatively high boiling point, into a lower boiling, more easily vaporizable or more volatile material, in order to produce a gasolene substitute therefrom, and a material which will be capable of direct use in an internal combustion engine and is related to my co-pending application Serial Number 564,142 filed September 21, 1931. Depending upon the nature and composition of the raw material operated upon, I may produce either aliphatic hydrocarbon mixtures, or carbocyclic hydrocarbon mixtures such as benzene its homologuesand isologues, or mixtures containing -members of both open chain 0 and closed chain hydrocarbons and derivatives therefrom.

By means of my invention, mixtures of hydrocarbons of relatively lower boiling points are obtained and hydrocarbon mixtures boiling at relatively higher temperatures, andnot only are suitable mixtures of oil vapor containing little or' no tarry matters obtained, but the process may be operated continuously, in the absence of entering steam into the mixture and at normal or elevated atmospheric pressures, thus obviating the necessity for the employment of intricate and costly equipment, and admitting of a product being continuously produced of uniform range of physical constants and rate of com- 35 bustion.

As suitable raw material I may employ, in addition to those mineral oils containing paraiiins or parafiin bases primarily or alone, other bodies such as asphalts or fractions, distillates or residues therefrom, or oils containing aromatic substances such as crude creosote or creosotic bodies, crude naphthalenes and naphthalenic bodies, etc., for the production of benzene (CSHG) and other hydrocarbons, and the preparation of technical and medicinal products.

In the following description, I make use of the term hydrocarbon in a general sense to designate mixtures such as mineral oils, shale oil, schist oil, and asphaltic bases, as well as residues, fractions and distillates therefrom and the like, being suitable raw materials applicable to my process to be herein described.

One of the objects of this invention relates to an improved continuous heat treatment for hydrocarbons and the manufacture therefrom and thereby of a highly refractive, very mobile, volatile and inflammable spirit, which has a wide solvent power for a large number of chemicals and substances in addition to its value as a gasolene or substitute therefor.

One of the principal obstacles encountered in processes of this nature heretofore has been the deposition of carbon on the inner surfaces of the pipes in the apparatus in which the oil is heated, which not only renders it increasingly diflicult to transmit external heat through the walls of the chamber or pipes to the interior, but thecarbon has ultimately clogged up the passages to the point where the apparatus has been rendered ineffective or inoperative. This and similar difiiculties are obviated in my process or are apparent to such a minimum degree as not to seriously interfere with the operating efficiency of the process as a whole. In my process herein described, the relatively small amount of carbon formed seems to be in a colloidal or highly dispersed condition, which does not deposit upon the walls of the pipe or apparatus, at least not in an objectionable amount.

The commonly used modes of treating petroso leum are reflux distillation followed by progressive distillation, generally fractional, in which the difierent hydrocarbon compounds and mixtures (the so-called cuts) are successively distilled ofi in the order of their relative volatility.

One method of carrying my process into eflect is illustrated in the attached drawing, in which the oil to be cracked enters through pipe 1, pump 2, pipes 3 and 4, into an open space tower 5 where it is preheated by the rising mixed hydrocarbon vapors and catalyzer gases, serving at the same time to condense the heavier boiling uncracked portion and to contact with the catalyzer placed in gas form in the same zone. This oilcatalyzer mixture is introduced in a direct way through pump 6 and pipe 7 over contact plates 8 in the heating apparatus 9.- This results in the advantage that the catalyzer tends to agglomerate or crystallize in tower 5 by means of cooling and thereby becomes admixed with the introduced crude hydrocarbon product, which is pumped out of tower, 5, and obviates the possibility of settling or depositing on the lower por-= tion of the tower.

In the heating unit 9, the hydrocarbon oils are in intimate contact with the catalyzing material, heated with or without pressure to the desired temperature range of 350-1300 F., and the here produced hydrocarbon vapors and catalyzer gases are led back, passing contact plates 8 110 ing apparatus 9, thereby assuring contact of maximum intimacy. A further means of agitation is by pumping the catalyzer-oil mixture through pipe 12, pump 13', pipe 14 and 16, and valve 40, back into heating apparatus 9.

Through setting of the relief valve 38 at about 28 lbs. pressure above the pressure in the cracking apparatus, the possibility is given that a portion of the uncracked or only partially cracked high saturated residue oil is withdrawn from system by way of pipe 14, valve 15, cooler 17, discharge pipe 18, and can be used for the production of high grade lubricating oil. At the same time, a portion of theresidue oil can be led through valve 33, pipes 34 and 36 into the oil burners and 37.

The low boiling hydrocarbons are partly fractionated in tower 5 by means of control head 19 and introduced through pipe 20 into the final fractionating tower 21, which is equipped with,

bubble plates or chemical rings not shown, and

there fractionated into the desired cuts or fractions. The final gasolene vapors are led through control head 22, pipe 23 into condenser 24 here being condensed and liquefied, and the finished productgasolene or motor fuelflows through the gas separator 25, and pipe 26, out of the system.

This eventually forms fixed gases which are led through pipe 2'7 to recovery, or may be burned under the still.

If with the uncondensable gases, it can be replaced into the process without interruption through filling tank 32. A part of the crude oil can be used to spray the catalyzer through valve 30 and pipe 31 out of tank 32 into the heating apparatus 9.

In the fractionating tower 21 the condensed heavier products are mixed by way of pipe 28, valve 29 in pump 2 with the crude oil, and thus re-introduced into the process through pipes 3 and 4. Nitrosyl chloride is introduced from pressure tank 41 through valve 42, pipe 43 into pipe '7, and mixes here with the catalyzer-oil mixture, passing over contact plates '8 into heating apparatus 9 and here re-activates the catalyzer.

My improved method, which is continuous, comprises catalytic'and distillatory actions, thereby forming lower boiling and more valuable compounds from higher boiling and less expensive mixtures. It comprises heating the raw material containing hydrocarbons by means of any appropriate source or heat, applied in,an advantageous manner, whereby the vapors are condensed by means of' a reflux condenser, the mechanical arrangement and preferred method of operation, being specified, ,claimed and illustrated in my copendlng application.

The amount and'physical and chemicalcon stants of the fraction or fractions obtained by depending upon (1) the nature ofthe hydrocarhon raw material; (23 The heating temperature:

(3) The constants of the materials obtained in is carried out, and the physical constants desired in the finished product.

As catalytic material I prefer to use a halogenated oxide of nitrogen, in the presence of aluminum halide, the least expensive of the halogens and an appropriate halogen to use in this connection, a nitrogen oxychloride or nitrogen chlor oxide such as nitrogen mono-oxide monochloride (NOCl) sometimes called nitrosyl chloride, having been found especially satisfactory. The nitrosyl chloride is never used alone, but always in conjunctionwith the haloid compound of a metal of Group III of the Mendeleefi System of Periodicity of the Elements, of which the least expensive of the elements in this group in haloid or halide combination is aluminum, the chloride of which has been found satisfactory for use in combination with nitrosyl chloride for the transformation of relatively higher boiling hydrocarbons into those of relatively lower boiling point by means of my invention. However, I have not obtained as satisfactory results by the use of nitrosyl chloride alone,'that is, in the absence of no absorbent material such as silicon dioxide, or absorbents in which silicon dioxide has been partially or wholly replaced by other bodies. as asbestos or other aluminum or magnesium containing bodies, being necessary in my process. I prefer to use that chloride of aluminum known as aluminum trichloride, with a halide of Group VIII of the Periodic Elements, preferably in the substantially anhydrous condition, and in conjunction with nitrosyl chloride as an activating, re-activating or rejuvenating agent. I have found that the catalytic power of aluminum chloride or similarly acting bodies upon petroleum products remains unimpaired for an indefinite period under the conditions comprehended in this invention, where nitrosyl chloride is brought in contact therewith as set forth herein.

I have obtained satisfactory results also by using boron trifluoride, boron tribromide and/or Of thefelements comprising Group V111 of the PeriodicElements to be used in conjunction with aluminum halide, iron in the form of iron halide, as iron chloride; preferably in the ferric condition has proven more satisfactory, the ferric chloride being introduced into the petroleum product either separately or with the aluminum chloride. v

This process is especially applicable to the treatment of gasoline ,residues from crude natural oils or t e crude oil obtained from cracking, where it is desired to obtain more'volatile hydr ocarbon mixtures from less volatile'hydrocarbon compounds and combinations.

lee

The commercial form of nitrosylchloride, alu

minum chloride, and ferric chloride isisufliciently pure and concentrated for the purposes of carrying out this invention.

Of the several ways of carrying my invention into practical effect and employing nitrogen oxychloride in conjunction with a halogen compound of Group III and of Group VIII of the chemical elements. The following example is 11- lustrative of one method, and this example is based upon the use of any gasoline residue or other similar residue, or residue from which the gasoline fraction has been partially or wholly removed, as obtained from natural petroleum, it being understood that the materials employed with the hydrocarbon raw material used will vary in quality and in steps, degree and speed of operation depending upon the constants of the raw material used, and the constants desired in the finished material.

Based upon a 100 pound initial charge of raw material is starting the continuous process, this is placed in the heating chamber and 5 to 12 pounds of combined aluminium and ferric chlorides incorporated therewith in any convenient manner whereby a homogeneously appearing admixture results. Or the aluminum chloride orthe ferric chloride or both, may be admixed with the charging stock outside the heating chamber. The chlorides may be admixed with the charging stock at room temperature and subsequently heated, or admixed with the heated charging stock. The cracking temperature lies within the range 250 700" F. for the majority of raw materials operated upon, and when the mass in the heating chamber has been heated to incipient cracking of the hydrocarbon material therein, nitrosyl chloride is admitted, intermittently, or preferably in a continuous manner, in the ratio of about two to three ounces to each 5 pounds metallic chlorides therein.

The admission of nitrosyl chloride is continuous in the ratio of about 4 to 5 ounces per 100 pounds of charging stock introduced after the process has become reactive. The aluminum chloride or the iron chloride does not require renewing, at least, in one series of over one hundred successive treatments of definitely introduced amounts of nitrosyl chloride and charging stock as above illustrated, the catalyst of aluminum and iron chlorides had apparently not been reduced in its desirable catalytically acting capacity. My process therefore, comprises in its broad scope the continuous or perpetual fortification or rejuvenation or reactivation of a mixture of aluminum chloride and iron chloride as a catalytically acting body in changing relatively high boiling hydrocarbons to relatively lower boiling ones, by means of' the continual introduction of definite amounts of nitrosyl chloride into a heated chamher in which is present the catalyst and the prodacts of its decomposition, and in which, is-being introduced in a continuous manner, definite amounts of charging stock relative to the amount of nitrosyl chloride entering the heated chamber.

I am aware that incident to the reactions involved, the chlorine in the nascent or superreactive state combines with a proportion of iron of which the heating chamber is wholly or partially constructed so that there is present after the operation has proceeded for a time, a proportion of iron chloride in addition to aluminum and iron chlorides originally added thereto, but the presence of this additional amount of iron compound is not detrimental to the process. However, it has been found that neither the aluminum chloride or the iron chloride does not reactivate,

at least, to the degree or point desired until a temperature above 250 F. has been reached.

Only atmospheric pressure, or a relatively low pressure above atmospheric is used, and no steam or other form of water, or water vapor, is introduced at any time into the heated chamber.

This method may be modified accordingto the relative refractivity of the raw material, its composition, the degree of heat applied, and the temperature of the cut or fraction it is desired to obtain. The amount of nitrosyl chloride introduced into the reacting chamber in the operation may also depend upon the relative refractivity and physical constants of raw material operated upon and the constants desired in the finished material, as is well known to those conversant with this particular art. The ratio of aluminum chloride to iron chloride is about 50-50, but on account of the formation of small amounts of iron chloride by the action of chlorine upon iron comprising the apparatus, I find that the initial introduction of aluminum chloride to 40 of iron chloride is usually preferable.

The above example is given for illustrative purposes only, and may be varied within comparatively. wide limits and still conserve the essence and spirit of my invention, which is the decomposition of hydrocarbons of relatively high boiling point into those of relatively lower boiling point by a heat treatment in the presence of a catalyst continually being reactivated or re.- juvenated by admission thereto and commingling therewith of nitrosyl chloride. It will readily be understood by those conversant with the art to which this invention appertains, that the composition of the hydrocarbon initially used, both as to its physical constants and chemical composition; the time and temperature to which it is heated during the reflux period of distillation, and the speed of fractionation and the boiling points and volatility of the fraction or several fractions obtained, together with the speed of introduction of nitrosyl chloride relative to the amount of charging stock introduced into the reaction chamber per unit length of time, will modify the process or the steps of the same, which is to obtain as a final product a substantially colorless and highly volatile liquid suitable as a substitute for gasoline.

Having now described my invention for continuously obtaining hydrocarbons of relatively low boiling point from hydrocarbons of relatively higher boiling point by heating the same in the presence of catalyst of halide compounds of Groups III and VIII of the "Periodic System of Elements reactivated by nitrosyl chloride, what I claim as new and desire to secure by Letters Patent is:- V

1. A process for the continuous conversion of high boiling petroleum fractions comprising heating the same in a chamber to a temperature or 250700 F. with a halogenated oxygen compound of nitrogen and an aluminum and iron halide in amount not exceeding twelve percent by weight of the original charge, until a gasoline substitute is obtained.

2. A process for the continuous conversion of high boiling hydrocarbons comprising heating the same in a chamber to a temperature of 250-700 F. with a mixture of aluminum chloride and iron chloride in the presence of nitrosyl chloride until a suflicient amount of relatively lower boiling fraction has been formed.

3. A process for the continuous cracking of hydrocarbon products comprising heating the same 150 in a chamber to a cracking temperature above the point of distillation and not to exceed 700 F. and in the presence of aluminum and iron chlorides which chlorides are being continually re-activated by the presence of nitrosyl chloride until a sufficient amount of relatively lower boiling fraction has been obtained.

4. A process for the continuous distillation of petroleum products comprising heating the same in a chamber to a cracking temperature around 600 F. with aluminum and-iron chlorides the chlorides being rejuvenated by the continual introduction therein of a proportion of nitrosyl chloride, definite as compared with the amount of unacted upon initial charge being introduced into the reaction chamber uniformly and simultaneously with the introduction of nitrosyl chloride,

' and removing the relatively lower boiling portion from the zone of reaction.

5. A process for the continuous decomposition of petroleum residues comprising heating the same in a chamber to a crackingtemperature between 250 F. and 700 F. with aluminum and iron chloride catalyst, reactivating said catalytically acting body by the continuous and uniform introduction of nitrosyl chloride into the reacting chamber, continuing the process until the amount of lower boiling fraction desired has been obtained.

6. A process for the continuous cracking of pepetroleum products to obtain therefrom products having a relatively lower boiling point and suitable as a substitute for gasoline, comprising heating said products in a reaction chamber with a mixture of iron and aluminum chlorides to the desired cracking temperature between 250 F. and 700 F. reactivating the chloride catalyst employed by the uniform and continuous introduction of nitrosyl chloride, in a definite amount respective to the amount of charging stock being continuously introduced in the reaction chamber, removing the lower boiling point fractions as desired and continuing the operation for an indefinite period.

8. In a process forthe continuous production of relatively lower boiling point aliphatic hydrocarbons from relatively higher boiling petroleum products, comprising introducing into a. heated reaction chamber about 6 pounds aluminum chloride, 5 pounds ferric chloride and pounds charging stock and after the whole has been heated to a temperature between 250-700" F. admitting into the reaction chamber a definite amount of nitrosyl chloride in a continuous manner, together with the continuous introduction into said chamber of a definite amount of charging stock relative to the amount of nitrosyl chloride being admittedfthe temperature of the reaction chamber being meanwhile kept below 700 F., continuing introduction of nitrosyl chloride troleum-containing mixtures comprising heating and charging stock with removal of formed relatively lower boiling point hydrocarbons for an the same in a chamber to a cracking temperature not exceeding 700 F. in contact with a mixture of iron and aluminum chlorides as catalyst,

re-activating the catalyst by the continuous introduction into the reacting chamber of a definite amount 'of nitrosyl chloride simultaneous with the introduction therein of a definite amount of charging stock, removing the formed lower boiling point hydrocarbons, continuing introduction of nitrosyl chloride and charging stock until the amount of relatively lower boiling materials have been obtained in amount desired.

7. A process for the continuous treatment of indefinite period.

9. The use of nitrosyl chloride as an activating agent in the treatment of petroleum products by a distillation process within the range 250-750 F., in conjunction with a mixture of aluminum and iron chlorides in the cracking of petroleum products into a mixture of relatively lower boiling point products suitable for motor fuel purposes, and in a continuous manner for an indefinite period of time as herein set forth. 

